Composition and method for color printing of resinous films



Patented Aug. 17, 1954 d COMPOSITION AND METHOD FOR COLOR PRINTING IOF RESINOUS FILMS Joseph M. Kuhn, Haddonfield, N. J., assignor to The Sherwin-Williams Company, Cleveland,

Ohio, a corporation of Ohio '1 No Drawing. Application May 16, 1951,

Serial N0. 226,745

19 Claims. 1

This invention relates, as indicated, to the art of decorating synthetic films, sheets, or articles, and more particularly to printing pastes especially adapted to the decorating of such films, sheets, or articles.

In the past few years there has been a tremendous growth in the popularityof plastic sheeting in the form of shower curtains, drapes, window curtains, seat covers, table covers,etc. Although these articles have been artistically decorated, the method of applying these patterns to the film or surface has not been altogether satisfactory. Such films are usually decorated by printing with conventional inks and paints in which the pigments are dispersed in aisolution ofa vinyl copolymer together with a solvent, such as aketone, e. g., methyl ethyl ketone, or isophorone. There are numerous difficulties with such a method of decorating plastic films. First, there isa fire hazard due to the presence of volatile solvents in the inks and the necessity for using organic solvents to clean the equipment. Also, there is the undesirable presence of solvent fumes resultingfrom the printing operation and the drying operation. In order to obtain a satisfactory bond, it is frequently necessary to heat the article up to a temperature at or near the fusion or softening point. Moreover, because of residual solvents in the inks, it is usually impossible to roll the printed sheetingwithout using paper slip-sheets. Unless such paper insert is used, the tackiness of the printed image and the pressure on theroll causes off-set printing on the back of the plastic film.

Another difficultywhich has been observed is that when the inks used in the prior methods of decorating dry, they apparently shrink somewhat and cause puckering of the plastic sheet.

.Still another disadvantage of the prior meth-.

od is the requirement of a relatively large selvage edge. This is necessary because on drying at the elevated temperatures heretofore. employed, there is a. considerable curling of the edge of the sheet.

It has been found that the foregoing difiiculties can be substantially eliminated by using an emulsion system of the oil-in-water type instead of the conventional ink or printing compositions which contain organic solvents to form a homogeneous single liquid phase system. In the new printing compositions, the pigment binder is a latexwhich, in the preferred cases, has a chemical nature corresponding closely to that of the sheet being printed. For example, where the film is a vinyl halide resin, e. g., vinyl chloride-vinyl acetate co-polymer, then the most satisfactory latex to be employed in the manner hereinafter explained will be a vinyl chloride latex.

The water system of printing on plastic films, as this invention maybe designated, represents a major advance in the art. No hazardous solvents are necessary, and the equipment may be cleaned with water. Printing pastes are readily removed from workers hands and clothing. Remarkable adhesion of the printed image to the plastic article is obtained. Improved sharpness of print has also been noted. From an economic standpoint it is now possible 5:130 save up to per yard by eliminating the slip-sheets. The printing compositions of this invention may be dried with great speed, thereby enabling the rolling of the printed stock without encountering off-set printing. The difzogficulty of puckering of the plastic backing sheet has been obviated, and no selvage edge is required.

These objectives are substantially fulfilled by the compositions and methods of this invention.

Other objects of this invention will appear as the description proceeds. To the accomplishment of the foregoing and related ends, said invention, then, consists of the means hereinafter fully described and particularly pointed out in the appended claims, the following description setting forth in detail certain illustrative embodiments of the invention, such disclosed means constituting, however, but a few of the various forms in which the principle of this invention may be employed.

Broadly stated, therefore, this invention comprises the provision of a printing paste composition for vinyl resin-containing plastic films, sheets and articles which comprises an oil-in- Water type emulsion of a terpene alcohol, and a hydrophilic salt of the condensation product of a monovinyl benzene and a substance selected from the group consisting of maleic acid, maleic anhydride, and partial esters of maleic acid, a solubilizing aliphatic alcohol of from 4 to 14 carbon atoms, and a vinyl resin latex. More particularly, this invention comprises a method for decorating such plastic films, sheets or articles which comprises the steps of applying to the surface thereof by a suitable printing method, such as, intaglio, raised roll, or screen printing processes, the printing paste described above, and substantially evaporating therefrom the aqueous phase by the application of heat or other suitable means. This invention also contemplates such plastic films, sheets, or articles which are coated with the printing compositions of this invention.

METHOD OF MAKING THE PRINTING PASTES phase initially carries a water soluble salt f-orming material, such as, an alkali metal hydroxide or, preferably, a water soluble amino compound. This phase may in certain instances desirably contain a water adsorptive clay, such as, bentonite or other such montmorillonite type clay. The pigments are usually present as an insoluble dispersed phase in the organic portion of the emulsion by reason of having been flushed from an aqueous dispersion. In certain other instances, however, the pigments are dry ground into the organic vehicle.

The monovinyl benzene-maleic co-polymer referred to above is conveniently produced by any one of several established ways.' The ingredients may be mass polymerized by heating, for example, styrene and maleic anhydride at temperatures between about 100 F. and 300 F. for several hours or more. In certain instances it may be found desirable to employ a small amount, e. g., 0.1% to 1.0% by weight of divinyl benzene in the (to-polymerization reaction. A peroxide catalyst is often used and it is desirable that the materials be heated with care as by means of a Water bath. Another method of producing these materials is by conducting the copolymerization in the presence of a solvent for the starting materials and the final product, such as, acetone. Instead of styrene, substituted styrenes including alkylated styrenes, such as,

methyl, ethyl, propyl and butyl styrenes, or sub-' stituted styrenes, such as, chlorostyrene, or the like may be used to prepare the co-polymers. Instead of maleic anhydride, there may be used partially esterified maleic acid, such as, the half esters methyl maleate, ethyl maleate, isopropyl maleate, sec. butyl maleate, etc. Further discussion of the production of these materials may be found by having reference to the patent to Barrett, 2,537,018, dated January 9, 1951; the patent to Seymour, 2,533,635, dated December 12, 1950; and the patent to Condo et 2.1., 2,286,062, dated June 9, 1942. It has been found that when using divinyl benzene as a cross-linking agent in these co-polymers, substantially larger amounts than those indicated above tend to cause the printing paste to become too viscous.

To compound the printing pastes, the most usual procedure is to pre-mix the monovinyl benzene-maleic material with the terpene alcohol and a solubilizing aliphatic alcohol, e. g., butyl alcohol, to make a stock solution. An aqueous dispersion of the desired pigment, such as may be made by dispersing a water insoluble pigment press cake in Water in the presence of a suitable dispersing agent, e. g., sodium lignosulphonate, is then mixed with the stock solution and the pigment flushed into the organic phase. For a more complete understanding of the flushed pigment technique, reference may be had to U. S. Patent 1,986,029. Thereafter a water dispersion or solution of a salt forming, basic acting material, preferably an amine, such as, morpholine, is added to the pigment dispersion and the ingredients well mixed. To this mixture is then added the latex emulsion after which the paste is diluted with water, or .a water-bentoni'te suspension, to the desired consistency. The amount of such montmorillonite clay employed is on the order of about 2% by weight of the entire composition.

One of the highly advantageous features of the compositions of this invention is that the latex emulsion is not coagulated by the addition of the other ingredients. Ordinarily, pigments will adsorb the dispersing agents in latex emulsions thereby causing the emulsion to break and the latex to coagulate. Although this has previously been obviated by the use of proteins in compositions containing a drying oil, such protective colloids are unnecessary in these printing pastes.

Other methods of making the printing pastes may be employed, however, as may be convenient in view of the nature of the pigment. If the pigment is a dry color, for example, then the flushing operation is not necessary and the pigments may be ground by ordinary means into the organic phase.

It becomes convenient to illustrate the methods of making the printing pastes of this invention by specific examples which are to be understood as merely illustrative of a preferred method of making the paste.

THE STOCK SOLUTION This solution is, in the preferred case, a premixed blend of a monovinyl benzene-maleic anhydride condensation product in a terpene alcohol, such as, alpha-terpineol or pine oil. Since the monovinyl benzene-maleic anhydride product is not soluble in pine oil or alpha-terpineol alone, a solubilizing aliphatic alcohol of from 4 to 14 carbon atoms is desirably employed in an amount sufficient to effect solution.

The terpene alcohol is preferably a monohydric terpene alcohol, such as, alpha-terpineol, or the fraction from pine trees known as pine oil and boiling at C. to 215 0., the chief component of which is alpha-terpineol (50% to 60%). This ingredient serves a number of important functions in these compositions. It controls foaming, serves as a diluent for the monovinyl benzenemaleic material in the presence of the alcohol solubilizer, reduces the amount of alcohol required, and yields a stable emulsion. It also serves as a retardant solvent when pigments are dry ground into the stock solution.

The alcohol component, or solubilizing agent, is generally and preferably an aliphatic alcohol containing from 4.- to 14 carbon atoms. Such alcohols may be straight chained, branch chained, cycloaliphatic, mixed aliphatic cycloaliphatic, primary or secondary alcohols. Specific examples of such solubilizing alcohols include butyl alcohol, amyl alcohol, tertiary amyl alcohol, hexyl alcohol, cyclohexyl alcohol, methyl cyclohexyl alcohol, ethyl cyclohexyl alcohol, octyl alcohol, 2-ethyl hexyl alcohol, capryl alcohol, decyl alcohol, lauryl alcohol, lorol, etc. The preferred alcohols have the general formula R--OH wherein R is alkyl and saturated, and contains from 4 to 8 carbon atoms. However, unsaturated alcohols and substituted aliphatic alcohols containing substantially unreactive substituent groups, such as, ether groups, as in butyl Cellosolve, and inorganic substituents such as,

halogen in the omega position, e.. g3, omega 1 Example I l 7 parts of styrene-maleic anhydride conden sation product were mixed with 7 parts of pine 011. To this mixture was added a sufiicient amount of butylfalcoholto' dissolve the styrenemaleic anhydride condensation product in the pine oil. In this case, 6 parts of butylalcohol were so used.

Note should be made of the fact that if too much of the solubilizing alcohol is used, the emulsion to be prepared subsequentlyfrom the stock solution may tend to be unstable.

Emample II y Equal parts of styrene-'maleic anhydride condensation product and pine oil were admixed, To this was added sufficient methyl cyclohexanol to dissolve the styrene product completely, in this case 0.? part per 2 parts of admixture.

Example III 1 6 parts of alpha methyl styrene-maleic anhydride condensation product and 7 parts of ,alpha terpineolwere admixed. To this was add *ed sufiicientcapryl alcohol to dissolve the styrene product completely. l l l l It will be seen, therefore, that the stock solution may be composed of about equal parts of a monovinyl benzene-maleic anhydride (or equivalent) condensation product and a terpene alcohol, with enough added solubilizing alcohol to make a homogeneous solution. None of these properties is critical as more or less of the styrene-maleic material may be used, and, as will be seen hereinafter, larger quantities than provided by a 1:1 ratio of the terpene alcohol to styrenemaleic product may also be used. In the final product, pine oil or the like is usually added, and the amount of monovinyl benzene-maleic condensation product is dependent to some extent upon the nature of the pigment which isem ployed. It hasbeen found, however, that with a 1:1 ratio, the amount of solubilizing alcohol required is at about the optimum for producing a stable emulsion in the final product. The required amount of solubilizing alcohol is determined by adding the alcohol in small additions to the mixture of terpene alcohol and monovinyl benzene-maleic condensation product until solution is obtained.

'FLUSI-IED COLOR PRINTING PASTES added water mixed with a salt forming, basic acting compound, such as, morpholine, methylamine, ethylamine, orthe like. This material then reactswith the acidic group or groupsin the monovinyl benzene-maleic condensation,

product to forma hydrophilic salt having emulsi fying properties.

For the purposes of this invention, the ali phatic amines and particularly those which are capable of volatilizin after application and during the drying operation, e. g, those having a boiling pointno. more than about l l0 C. are to be preferred; Specific examples of such agents includeammonia, alkyl. amines, such as, methyl amine, ethyl amine, diethyl amine, propyl amine, isopropyl amine, mixed isopropyl amines, butyl amine, and cyclic imines, such as, morpholine, piperidine, pyrrole, pyrrolidine, and the like. All of the foregoing amino compounds may be considered as primary or secondary aliphatic amines having the general formula:

where R and R are each selected from hydrogen, aliphatic monovalent radicles, and aliphatic divalent radicles having the free valences united. Another way of stating the same thing is that the aliphatic amines useful herein are selected from those having the general formulas:

' R-N-R 3 I l and R"= NH wherein R and R are, each selected from hydrogen and aliphatic radicles, and R is abivalent taliphatic radicle having its free bonds attached Less desirable, although satisfactory for certain purposes are the alkali metal salt forming materials, such as sodium hydroxideand potassium hydroxide. The wash fastness of the material is unsatisfactory when such materials are employed because the hydrophilic or water solubilizing portion of the monovinyl benzene-maleic condensation product salt is not volatilized during the drying operation. Although ammonia is satisfactory from the standpoint of providing a water soluble salt of the monovinyl benzene-maleic condensation product which on drying decomposes to liberate ammonia and yield a product of satisfactory wash fastness, ammonia has a tendency to be released from the printing baths and on a large run will create an odor and handling problem. There is also some tendency for the emulsion to break when a sufficient amount of ammonia has thus escaped. Best results are obtained, therefore, when the volatile aliphatic amino compounds, such as, morpholine and ethyl amine are used,

After the salt forming agent is added,the mixture is agitated until smooth and free of any lumps. Thereafter, the latex is mixed into the formulation. This concentrated pasteis then diluted with water or a water-bentonite suspension to the desired consistency for printing.

Specific examples of printing paste formula,- tions of various colors are as follows, these being illustrative, however, of but one method of formulating the novel compositions of this invention.

Example IV 169 lbs. of Aqua Black B paste (Carbon Black) and 22 lbs. of water are mixed to disperse the pigment material. To this dispersion are added 98 lbs. of stock solution (Example I) and 27 lbs. of pine oil. The pigment is then. flushed into the organic phase and 86 lbs. of water are separated and removed. To this are then added 186 lbs. of water containing dispersed therein 34 lbs. of morpholine. The entire mass is then 7 mixed smooth and free of any lu'mps. An additional 50 lbs. of water are added, and then 200 lbs. of vinyl chloride latex containing 55% solids are introduced into the mixture. Thereafter a pre-mixed dispersion of 280- lbs. of water and 20 lbs. of bentonite are added and the entire mixture stirred to printing consistency. It should be noted that after the morpholine, or other such alkaline reacting agent has been added, there is obtained an oil-in-water emulsion.

The bentonite serves as a suspending agent and a delustering agent. While this ingredient is not essential, it has been found that bentonite, or the montmorillonite type clay, is the only type of clay that works satisfactorily in these compositions.

Example V Red Violet.Following the same procedure set forth in Example IV above-357 lbs. of Harmon Textile Red Violet Paste (Thioindigo Red 3B, Color'Index #1212) containing 60 lbs. of the dry pigment, and 24 lbs. of water were mixed to dispersethe pigment. 90' lbs. of the stock solution of Example I and 40 lbs. of pine oil were added and the pigment flushed into the organic phase with the subsequent removal of 277 lbs. of water. A solution of 136 lbs. of water and 30 lbs. of morpholine was added and the mixture stirred until free of lumps. 100 lbs. of water and 200 lbs. of latex (vinyl chloride 55% solids) were also added. Again a pre-mixture of 280 lbs. of water and 20 lbs. of bentonite were stirred into the final mixture.

Example VI Yellow.Following the same procedure as set forth in Examples IV and Vabove, 235 lbs. of D2774 Permansa Yellow G Presscake (75 lbs. dry basis) and 'lbs. of a 50% aqueous solution of the sodium salt of the formaldehyde condensation product with naphthalene sulphonic acid were admixed to disperse the pigment. The sulphonate employed here is a dispersing agent and may be replaced by such other dispersing agents as the sulphonated lignins, etc. 112 lbs. of the stock solution of Example I were then added and the pigment flushed into the organic layer with the removal of 130 lbs. of water. 131 lbs. of water having dissolved therein 3'? lbs. of morpholine were added and the mixture agitated until free of lumps. 100 lbs. of water and 200 lbs. of latex (vinyl chloride 55% solids) were then added. As in the previous example a pro-mixture of, lbs. of bentonite in 280 lbs. of water was then added and the composition agitated to a smooth consistency. Permansa Yellow 10G is made by coupling diazotized 4-chloro-2-nitroaniline with acetoacet-Z-chloroanilide.

Example VII Green.--Following the same procedure as set forth above, the following ingredients in the amounts indicated were formulated.

Bentonite 20 lbs.

Permansa 1Green'B' Presscake is the iron salt of nitroso beta naphthol.

Example VIII BZue.-Following the same procedure as set forth in the previous examples, the following ingredients were formulated:

Monastral Blue is a copper phthalocyanine pigment.

DRY COLOR PRINTING PASTES When dealing with a dry pigment, such as, titanium dioxide; the procedure is somewhat modified over that illustrated previously in Examples IV through VIII. In general, a solution of the styrene-maleic condensation product is prepared in water by saponifying it with morpholine or ammonia, with a defoaming agent present. The dry pigment is mixed in followed by the latex and a sufficient amount of water to attain the proper viscosity. Additional defoaming agent may be added as required. Thereafter, the dry pigment is added to a portion of the preceding solution and then the balance of said solution added to the pigmented portion which is being mixed on a dispersion mixer. The latex is added and then a relatively minor amount of pine oil, or other such terpene alcohol is blended Specific examples of such dry color formulations are as follows:

Example IX White-264 lbs. of water and 33 lbs. of styrenemaleic anhydride condensation product were mixed together until thoroughly wetted. 33 lbs. of morpholine and 3 lbs. of octyl alcohol were added to the mixture and agitated until solution was obtained. Thereafter 285 lbs. of titanium dioxide were added to the solution in a dispersion mixer until a smooth paste is obtained. To this paste were then added 332 lbs. of vinyl chloride latex (55% solids) and. 50 lbs. of pine oil.

Example X CLEAR PRINTING PASTE It is frequently desirable to employ a clear printing paste as a diluent for the pigmented pastes and. also as a medium into which an organic dye material may be incorporated as another means of imparting color by the process of this invention. "For example, soluble dyes, such as, the well known fluorescent dyes, may be incorporated into the clear paste prepared according to the following example.

EXAMPLE XI Clean-.150 lbs. of the stock solution of Example I were mixed to smooth consistency with 200 lbs. of a bentonite-water paste. To this mixture were then added 300 lbs. of water and 50 lbs. of morpholine asa pre-mixed dispersion. The mixture was agitated until smooth and free of any lumps, and then 300 lbs. of a vinyl chloride latex containing 55% solids were added to yield 1000 lbs. of a clear paste.

The specific examples given above illustrate a manner in which flushed color pastes, dry color pastes, and clear pastes may be produced in accordance with this invention. For convenience in visualizing the relative amounts of the several ingredients contained in the preferred compositions of this invention, the following tables give an analysis of each of the foregoing printing compositions.

TABLE I.FLUSHED COLORS Example No IV V VI VII VIII Terpene alcohol. 61.3 71. 5 39. 2 51. 5 51. .25 Allphatic alcohoL. 29. 4 27 33.6 27 22. 5 Malelc product 34. 3 31. 5 39. 2 31. 5 26. 25 A 34 30 37 30 25 110 110 110 110 110 70 60 75 60 50 20 20 20 20 641 650 638. 5 670 670. 5 Dispersing agent 7. 5 l. 24. 5

Total l, 000 1, 000 l, 000 1, 000 1, 000

TABLE II.DRY COLORS Example No IX X XI Terpene alcohol 50 54. 9 52. 5 Aliphatic alcohol 3 33. 2 45 Maleic product. 33 38.9 52, 5 Amman. 33 40 50 Lawn. 182. 6 110 165 Plgmenh. 285 73 Bentonite. 20 20 Water 413. 4 630 615 Dispersing agent Total l, 000 1, 000 l, 000

A general picture of the preferred ranges for the various component of the compositions of this invention may be readily discerned from the foregoing tables. It will be noted that, in general, the amount. of the amine ingredient is, in the preferred case, about equivalent to the amount of the monovinyl benzene-maleic conclensation product when morpholine is employed as the amine. In using the various other amino compounds useful in these compositions, amounts approximately chemically equivalent to the morpholine are desired. For example, if diethylamine were to be used in place of 30 lbs. of morpholine, a chemically equivalent amount could be used. In the preferred cases, an amount of amine slightly in excess of that required to neutralize the acidity of the monovinyl benzene maleic product is employed since it is. desirable to take care of that which may be lost by evaporation during the printing process.

The ratio of terpene alcohol to monovinyl benzene-maleic condensation product ranges indicated previously, the amount of solubilizlng alcohol may vary between wide limits due to the variation in solubilizing power of the alcohols and the nature of the solvent and solute.

The ratio of latex to pigment, it will be observed, may vary from about 2:1 to about 1:2. Bentonite, which may be used as a filler and/or delusterant, is not an essential. component of the compositions and when used may be present in amounts approximating 2% of the entire composition.

These compositions are, as indicated, emulsions of the oil-in-water type, the water phase constituting from about 40% to as high as 70% of the entire composition, or, stated in another way, these compositions contain from about 30% to about solids.

Various blends of the foregoing printing paste compositions may be made for the purpose of producing different colors as. well as shades and tints. For example, one part of the reen printing paste of Example VII may be blended with ten parts of the white of Example X to provide a pastel tint of green. It will be seen, therefore, that a wide range of colors, shades and tints may be produced by blending the printing pastes exemplified above or similar printing apastes made using other conventional pigmentary materials or insolubilized dyes, such as, the well known daylight fluorescent pigments. Any Water-insoluble colorant may be employed as the pigment whether organic or inorganic so long as it is substantially inert chemically and physically in the environment in which it is employed. Zinc oxide, chrome green, ultramarine blue, chrome orange, titanium dioxide, the copper phthalocyanines, etc. may be used as well as the other types exemplified in the foregoing examples.

The foregoing examples have been confined to a vinyl chloride latex containing 55% solids as illustrative of the best mode of compounding the compositions of this invention. It is obvious that other latices containing anywhere from 30% up to as much as solids may be substituted in place of that given in the specific examples. It has also been found that latices which are produced from other vinyl halides, such as, vinyl fluoride or bromide, and co-polymers of such vinyl halides with vinyl acetate may be employed to replace part or all of the 100% vinyl chloride latex. It is desired that the chemical composition of the latex thus employed correspond closely with the chemical composition of the base plastic .to which it is to be applied. These compositions are particularly suited for application on plastic films, sheets, or articles which comprise a polymer or a co-polymer of a vinyl halide.

from approximately 1:1 to about 2:1, and, as

Specific examples of such plastic base materials include plasticized polyvinyl chloride-polyvinyl acetate films containing from to 98% vinyl chloride, polyvinylidene chloride, polyvinylacetal, polyvinylbutyral, polyvinylformal, co-polymerized vinyl chloride-polyvinylidene chloride, vinylidene chloride-vinyl cyanide co-polymers and the like. The compositions of this invention are also useful in coating other continuous surface n0n-fabric type resinous materials although the adherence of the dried film to the base material has not been found to be as satisfactory as with the vinyl halide or vinylidene halide containing resins.

The articles of this invention, i. e., the plastic base having imprinted thereon a design or coating resulting when the printing paste compositions of thisinvention are employed, possesses new and useful properties in itself in that the prior necessity for a large selvage edge in printing unsupported films is removed, no wrinkling or puckering is evident when the film has dried, and the adhesion obtainable through the use of these printing compositions is superior to that which has heretofore been secured.

In printing the plastic films, sheets or articles with these compositions, the usual printing machines, either intaglio or raised roll, or silk screen printing methods may be used to cast the paste on the base material. After the printing paste has been applied to the surface of the plastic, the material may be passed through a drying oven or into other suitable drying means to remove the water from the paste and dry the film. The temperatures employed for this purpose generally range from about 120 F. to 150 F. Thereafter, the printed sheeting may be rolled or stacked without the necessity of inserting a separatory sheet, or slip-sheet as is usually em.- ployed to prevent oif-set printing on the back side due to wet images and the pressure due to rolling or stacking. It is usual in drying the films to festoon them in a large room maintained at a preferred temperature of about 135 F. to 140 F. and remove the water slowly. Upon drying, the resin in the printed areas seems to unite to form a strongly adhering continuous film over the base plastic.

Other modes of applying the principle of this invention may be employed instead of those specifically set forth above, changes being made as regards the details as herein disclosed, provided the elements set forth in any of the following claims, or the equivalent of such be employed.

1, therefore, particularly point out and distinctly claim as my invention:

1. A printing paste composition for vinyl resin containing plastic films, sheets, and articles which comprises an oil-in-water type emulsion of a terpene alcohol, a hydrophilic salt of the condensation product of a monovinyl benzene hydrocarbon and a substance selected from the group consisting of maleic acid, maleic anhydride, and partial esters of maleic acid, an aliphatic monohydric alcohol containing from 4 to 14 carbon atoms, and a vinyl resin latex selected from the group consisting of homopolymeric vinyl halide resin latices and latices of co-polymers of vinyl halides and vinyl acetate.

2. A printing paste composition for vinyl resin containing plastic films, sheets, and articles which comprises an emulsion of the oil-in-water type wherein the oil phase comprises a solution of a hydrophilic salt of the condensation product of a monovinyl benzene hydrocarbon and a substance selected from the group consisting of maleic acid, maleic anhydride. and partial esters of maleic acid, in a terpene alcohol solubilized therein by an aliphatic monohydric alcohol containing from 4 to 14 carbon atoms, and a vinyl resin latex selected from the group consisting of homopolymeric vinyl halide resin latices and latices of co-polymers of vinyl halides and vinyl acetate, said oil phase having dispersed therein a water-insoluble pigment; and wherein the aqueous phase comprises water.

3. A printing paste composition for vinyl resin containing plastic films, sheets, and articles which comprises an oil-in-water type emulsion of a terpene alcohol, an amine salt of the condensation product of a monovinyl benzene hydrocarbon and a substance selected from the group consisting of maleic acid, maleic anhy dride, and partial esters of maleic acid, said amine having a boiling point of no more than about C., and said amine being selected from the group consisting of ammonia, alkyl amines and cyclic amines, an aliphatic alcohol containing from 4 to 14 carbon atoms, and a vinyl resin latex selected from the group consisting of homopolymeric vinyl halide resin latices and latices of co-polymers of vinyl halides and vinyl acetate.

4. A pigmented printing paste composition in accordance with claim 3.

5. A composition in accordance with claim 3 in which the terpene alcohol is alpha-terpineol.

6. A composition in accordance with claim 3 in which the terpene alcohol is pine oil.

7. A composition in accordance with claim 3 in which the amine is morpholine.

8. A composition in accordance with claim 3 in which the amine is ammonia.

9. A printing paste composition for plastic films, sheets and articles comprising a vinyl halide resin, which composition is an oil-in-water type emulsion wherein the oil phase comprises a solution of an amine salt of the condensation product of styrene and maleic anhydride, said amine having a boiling point no more than about 140 C., and said amine being selected from the group consisting of ammonia, alkyl amines and cyclic imines, in a terpene alcohol, said solution aided by a solubilizing amount of an aliphatic alcohol containing from i to 14 carbon atoms, a homopolymeric vinyl halide latex; and an aqueous phase comprising water.

10. A printing paste in accordance with claim 9 in which the vinyl halide is vinyl chloride.

11. A pigmented printing paste composition for plastic films, sheets and articles comprising a vinyl chloride resin, which composition is an oil-in-water type emulsion wherein the oil phase comprises a solution of the morpholine salt of the condensation product of styrene and maleic anhydride in pine oil, said solution aided by a solubilizing amount of butyl alcohol, a homopolymeric vinyl chloride latex containing from 30% to 65% solids, and a water-insoluble pigment dispersed in said oil phase; and an aqueous phase comprising water.

12. A process for printing on vinyl resins which comprises applying by ordinary printing means to a vinyl resin film, sheet or article a printing paste composition which comprises an oil-in-water type emulsion having as the water immiscible phase a pigment dispsersed in a solution of a terpene alcohol, a hydrophilic salt of the condensation product of a monovinyl ben- Zene hydrocarbon and a material selected from the group consisting of maleic acid, maleic anhydride, and partial esters of maleic acid, said salt being solubilized in said terpene alcohol by a solubilizing amount of an aliphatic monohydric alcohol containing from 4 to 14 carbon atoms, and a vinyl resin latex selected from the group consisting of homopolymeric vinyl halide resin latices and latices of co-polymers of vinyl halides and vinyl acetate and an aqueous phase comprising water, said composition containing from 40% to 70% water, and subsequently slowly evaporating the water at a temperature of from about 120 F. to F.

13. A process for printing on vinyl halide resins which comprises applying by ordinary printing means to a vinyl halide containing film, sheet or article, a printing paste composition which is an oil-in-water type emulsion wherein the oil phase comprises a solution of an amine salt of the condensation product of styrene and maleic anhydride, said amine having a boiling point no more than about 140 C., and said amine being selected from the group consisting of ammonia, alkyl amines, cyclic imines, in a terpene alcohol, said solution being aided by the inclusion of a solubilizing amount of an aliphatic alcohol containing from 4 to 14 carbon atoms, a homopolymeric vinyl halide latex; and an aqueous phase comprising water, said composition containing from 40% to 70% water, and subsequently slowly evaporating the water at a temperature of from about 120 F, to 150 F.

14. A process for printing on vinyl halide resins which comprises applying by ordinary printing means to a vinyl halide containing film, sheet or article, a printing paste composition which is an oil-in-water type emulsion wherein the oil phase comprises a dispersion of a waterinsoluble pigment in a solution of a morpholine salt of the condensation product of styrene and maleic anhydride in pine oil, said solution being aided by the inclusion of a solubilizing amount of butyl alcohol, a homopolymeric vinyl halide latex; and an aqueous phase comprising a suspension of bentonite in water, said composition containing from 40% to 70% of water, and subsequently slowly evaporating the water at a temperature of from about 120 F. to 150 F.

15, A process for printing on co-polymerized vinyl chloride-vinyl acetate resins which comprises applying by ordinary printing means to a vinyl chloride-vinyl acetate film, sheet or article, a printing paste composition which is an oil-in-water type emulsion wherein the oil phase comprises a dispersion of a water-insoluble pigment in a solution of a morpholine salt of the condensation product of styrene and inaleic anhydride in pine oil, said solution being aided by the inclusion of a solubilizing amount of butyl alcohol, a homopolymeric vinyl chloride latex; and an aqueous phase comprising a suspension of bentonite in water, said composition containing from 40% to water, and subsequently slowly evaporating the water at a temperature of about F.

16. An article of manufacture comprising a solid vinyl resin containing plastic base having imprinted thereover and strongly adhering thereto a smooth imprinted image which is the dehydration product of a printing paste having a composition substantially identical with the product of claim 1.

17. An article of manufacture comprising a solid vinyl resin containing plastic base having imprinted thereover and strongly adhering thereto a smooth imprinted image which is the dehydration product of a printing paste having a composition substantially identical with the product of claim 2.

18. An article of manufacture comprising a solid vinyl halide resin containing plastic base having imprinted thereover and strongly adhering thereto a smooth imprinted image which is the dehydration product of a printing paste having a composition substantially identical with the product of claim 9.

19. An article of manufacture comprising a solid vinyl fluoride resin containing plastic base having imprinted thereover and strongly adhering thereto a smooth imprinted image which is the dehydration product of a printing paste having a composition substantially identical with the product of claim 11.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,416,232 Soday Feb. 1:8, 1947 2,428,453 Feild Oct. '7, 1947 2,428,716 McGill et al. Oct. 7, 1947 2,467,352 Williams Apr. 12, 1949 2,536,018 Schoenholz et al. Jan. 2, 1951 2,536,470 Schoenholz Jan. 2, 1951 2,550,047 Durr et al. Apr. 24, 1951 

12. A PROCESS FOR PRINTING ON VINYL RESINS WHICH COMPRISES APPLYING BY ORDINARY PRINTING MEANS TO A VINYL RESIN FILM, SHEET OR ARTICLE A PRINTING PASTE COMPOSITION WHICH COMPRISES AN OIL-IN-WATER TYPE EMULSION HAVING AS THE WATER IMMISCIBLE PHASE A PIGMENT DISPERSED IN A SOLUTION OF A TERPENE ALCOHOL, A HYDROPHILIC SALT OF THE CONDENSATION PRODUCT OF A MONOVINYL BENZENE HYDROCARBON AND A MATERIAL SELECTED FROM THE GROUP CONSISTING OF MALEIC ACID, MALEIC ANHYDRIDE, AND PARTIAL ESTERS OF MALEIC ACID, SAID SALT BEING SOLUBILIZED IN SAID TERPENE ALCOHOL BY A SOLUBILIZING AMOUNT OF AN ALIPHATIC MONOHYDRIC ALCOHOL CONTAINING FROM 4 TO 14 CARBON ATOMS, AND A VINYL RESIN LATEX SELECTED FROM THE GROUP CONSISTING OF HOMOPOLYMERIC VINYL HALIDE RESIN LATICES AND LATICES OF CO-POLYMERS OF VINYL HALIDES AND VINYL ACETATE AND AN AQUEOUS PHASE COMPRISING WATER, SAID COMPOSITION CONTAINING FROM 40% TO 70% WATER, AND SUBSEQUENTLY SLOWLY EVAPORATING THE WATER AT A TEMPERATURE OF FROM ABOUT 120* F. TO 150* F. 